The reaction of the dinuclear phosphinito bridged complex [(PHCy2)Pt(μ-PCy2)κ2P,O-μ-P(O)Cy2Pt(PHCy2)](Pt-Pt) (1) with phenylacetylene affords the η1-alkenyl-μ,η1η2-alkynyl complex [(η1-trans-(Ph)HC[double bond, length as m-dash]CH)(PHCy2)Pt(μ-PCy2)(μ,η1η2-PhC[triple bond, length as m-dash]C)PtκP-P(O)Cy2(PHCy2)] (4) displaying a σ-bonded 2-phenylethenyl ligand and an alkynyl (μ-κCαη2) bridge between the platinum atoms. Complex 4 was shown to form in two steps initially, the attack of the first molecule of phenylacetylene gives the σ-acetylide complex [(PHCy2)(η1-PhC[triple bond, length as m-dash]C)Pt1(μ-PCy2)Pt2(PHCy2)κP-P(OH)Cy2](Pt-Pt) (5) featuring an intramolecular π-type hydrogen bond between the POH and the C[triple bond, length as m-dash]C triple bond; fast reaction of 5 with a second molecule of phenylacetylene results in the oxidative addition of the terminal C-H bond of the second alkyne to Pt1 that, after rearrangements, leads to 4. Selleck Opaganib When left in solution for two weeks, complex 4 spontaneously isomerizes completely to [(PHCy2)(η1-trans-(Ph)HC[double bond, length as m-dash]CH)Pt(μ-PCy2)κ2P,O-μ-P(O)Cy2Pt(η1-PhC[triple bond, length as m-dash]C)(PHCy2)] (7) displaying a 2-phenylethenyl ligand and a phenylethynyl group both σ-bonded to the metal. Density functional calculations at the B3LYP/LACV3P++**//DFT/LACVP* level were carried out to study the thermodynamics of the formation of all considered complexes and to trace the mechanism of formation of the observed products.As the activity of dimethyl ether (DME) carbonylation over mordenite proportionally correlates with the Brønsted acid sites (BAS) in 8-membered ring (8-MR), enhancing the concentration of BAS in the 8-MR of MOR is important to improve the efficiency of the reaction. Herein, we report that the distribution of the BAS in the zeolite catalyst H-MOR can be altered by the synthesis of H-MOR with different cyclic amine structure-directing templates, several of which have not been reported previously for MOR synthesis. By combining FTIR, ICP, TG analysis and DFT calculations, it is verified that the strength of the interaction between amine or sodium cations and [AlO4]- in the zeolite framework plays a decisive role in Al distribution, owing to the competitive effect between Na+ and the cyclic amine compensating negative charges from the framework [AlO4]-. Quantitative analysis of the BAS in the 12-MR and 8-MR identifies the optimum template for maximizing the BAS in the 8-MR. It is shown that the enhanced activity of the H-MOR for the DME carbonylation to methyl acetate correlates with the increase in the BAS in the 8-MR. Our finding thus provides a facile strategy to direct Al location within different channels of the zeolite, which must benefit spatially confined reaction systems.We propose a universal dimer-doping strategy to improve the photocatalytic water splitting activity of Ru1/TiO2 single-atom catalysts, in which the N atom is simultaneously doped. First-principles calculations show that the N dopants promote the substitution of Ti with Ru on the anatase TiO2(101) surface by chemical bonding between Ru and N, and increase the stability of the system. Isolated Ru1 atoms act as active sites for the reduction of protons, and Ru1-N1/TiO2 has a hydrogen evolution activity comparable to that of Pd. The impurity bands within the band gap lead to a significant red-shift of the absorption edge towards the visible region, improving the photoabsorption and photocatalytic performance of TiO2 under sunlight. The reason is the charge compensation effect localized to the doped Ru-N dimers. We expect that this generic scheme that simultaneously realizes band-structure tailoring and reaction control also applies to other single-atom loaded oxide-based photocatalytic systems.NiBr2 reacts with 3-hexyne in the presence of Mg and EtOH to give the cyclobutadiene bromide complex [(C4Et4)NiBr2]2, which serves as a general precursor for various cyclobutadiene nickel compounds. In particular, complexes with 2-electron ligands (C4Et4)Ni(L)Br2 (L = PPh3, P(OMe)3, pyridine), complexes with bidentate ligands [(C4Et4)Ni(L2)Br]PF6 (L2 = bipyridine, phenanthroline), and nickelacarborane (C4Et4)NiC2B9H11 were obtained from [(C4Et4)NiBr2]2 in 70-95% yields. The reactions of [(C4Et4)NiBr2]2 with an excess of strong ligands, such as tBuNC or dppe, led to the displacement of cyclobutadiene. The structures of the five compounds have been established by X-ray diffraction analysis. The previously reported data on cyclobutadiene nickel complexes have been also reviewed.An N-heterocyclic carbene triplatinum complex with two triply bridging sulfide ligands reacts with a silver(i) salt and affords a heptanuclear complex. X-ray crystallographic analysis revealed that a silver(i) ion connects two triplatinum complexes with one of the three Pt-Pt bonds of each triplatinum unit.Vanadium-based composite anodes have been designed for applications in alkali metal ion batteries, including lithium-ion batteries (LIBs), sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs). However, the problems of inferior long-term cycling stability caused by the large volume change and dissolution of vanadium-based active materials during cycles and slow diffusion for large radii of Na+ and K+ still limit their underlying capability and need to be addressed. In the present work, we initially designed and fabricated a vanadium nitride/carbon fiber (VN/CNF) composite via a facile electrospinning method followed by the ammonization process. The obtained VN/CNF composite anode exhibited excellent half/full sodium and potassium storage performance. When used as an anode material for SIBs, it delivered a high capacity of 403 mA h g-1 at 0.1 A g-1 after 100 cycles and as large as 237 mA h g-1 at 2 A g-1 even after 4000 cycles with negligible capacity fading. More importantly, the VN/CNFs//Na3V2(PO4)3 full cell by coupling the VN/CNF composite anode with the Na3V2(PO4)3 (NVP) cathode also exhibited a desirable capacity of 257 mA h g-1 at 500 mA g-1 after 50 cycles. Besides, when further evaluated as an anode for PIBs, the VN/CNF composite anode achieved a large capacity of 266 mA h g-1 after 200 cycles at 0.1 A g-1 and maintained a stable capacity of 152 mA h g-1 at 1 A g-1 even after 1000 cycles, showing significant long-term cycling stability. This is one of the best performances of vanadium-based anode materials for SIBs and PIBs reported so far.